Positive electrode active substance, positive electrode material, positive electrode, and non-aqueous electrolyte secondary battery

ABSTRACT

Disclosed is a positive electrode active substance for a non-aqueous electrolyte secondary battery including a composite oxide containing lithium and nickel, in which the positive electrode active substance has a structure of secondary particles formed by aggregation of primary particles. The average particle diameter of the primary particles (D1) is 0.9 μm or less. The average particle diameter of the primary particles (D1) and the standard deviation (σ) of the average particle diameter of the primary particles (D1) meet the relationship of D1/σ 2 ≧24.

TECHNICAL FIELD

The present invention relates to a positive electrode active substance,a positive electrode material, a positive electrode, and a non-aqueouselectrolyte secondary battery.

BACKGROUND ART

Currently, a non-aqueous electrolyte secondary battery including alithium ion secondary battery, which is used for a mobile device such asa mobile phone, is available as a commercial product. The non-aqueouselectrolyte secondary battery generally has a constitution that apositive electrode having a positive electrode active substance or thelike coated on a current collector and a negative electrode having anegative electrode active substance or the like coated on a currentcollector are connected to each other via an electrolyte layer in whicha non-aqueous electrolyte solution or a non-electrolyte gel ismaintained within a separator. According to absorption and desorption ofions such as lithium ions on an electrode active substance, charging anddischarging reactions of a battery occur.

In recent years, it is desired to reduce the amount of carbon dioxide inorder to cope with the global warming. As such, a non-aqueouselectrolyte secondary battery having small environmental burden has beenused not only for a mobile device but also for a power source device ofan electric vehicle such as a hybrid vehicle (HEV), an electric vehicle(EV), or a fuel cell vehicle.

As the non-aqueous electrolyte secondary battery for application to anelectric vehicle, it is required to have high output and high capacity.As a positive electrode active substance used for the positive electrodeof a non-aqueous electrolyte secondary battery for an electric vehicle,a lithium cobalt composite oxide, which is a layered composite oxide,has been already widely used since it can provide high voltage at thelevel of 4 V and has high energy density. However, due to resourcescarcity, cobalt as a raw material is expensive, and considering thepossibility of having dramatic demand in future, it is not stable interms of supply of a raw material. There is also a possibility of havingan increase in the raw material cost of cobalt. Accordingly, a compositeoxide having less cobalt content ratio is desired.

Similarly to the lithium cobalt composite oxide, a lithium nickelcomposite oxide has a layered structure but is less expensive than thelithium cobalt composite oxide. Furthermore, it is almost equivalent tothe lithium cobalt composite oxide in terms of theoretical dischargecapacity. From this point of view, it is expected that a lithium nickelcomposite oxide is used for constituting a battery with high capacityfor practical use.

With regard to a lithium ion secondary battery in which a compositeoxide containing lithium and nickel such as a lithium nickel compositeoxide (hereinbelow, also simply referred to as the “lithium nickel-basedcomposite oxide”) is used for a positive electrode active substance,charging and discharging are performed according to desorption andinsertion of lithium ions from and to the composite oxide. At that time,since the composite oxide undergoes shrinkage and expansion inconjunction with the desorption and insertion of lithium ions, there areproblems in that a great decrease in capacity occurs in accordance withrepeated charge and discharge cycles by a factor such as the collapse ofthe crystal structure. There is also a problem in that a decrease incapacity becomes significant when the battery is used for a long periodof time.

In view of the aforementioned problems, in JP 2001-85006 A, for example,a technique of forming secondary particles in a lithium nickel compositeoxide with relatively large primary particles is suggested for thepurpose of improving discharge capacity and cycle characteristics.

SUMMARY OF THE INVENTION

However, even with the technique described in the Patent Literature 1,the improvement of cycle characteristics was not sufficient.

Under the circumstances, an object of the present invention is toprovide, with respect to a non-aqueous electrolyte secondary battery, ameans capable of suppressing a decrease in capacity when the battery isused for a long period of time, thus improving cycle characteristics.

In this regard, the inventors of the present invention conductedintensive studies. As a result, they found that the aforementionedproblems can be solved when the composite oxide containing lithium andnickel as a positive electrode active substance for a non-aqueouselectrolyte secondary battery has a structure of secondary particlesformed by aggregation of primary particles, the value of the averageparticle diameter of the primary particles is controlled in a specificrange, and having the average particle diameter of the primary particlesand the standard deviation of the average particle diameter of theprimary particles meet a predetermined relationship. The presentinvention is completed accordingly.

Specifically, according to one aspect of the present invention, apositive electrode active substance for a non-aqueous electrolytesecondary battery, the positive electrode active substance comprising acomposite oxide containing lithium and nickel, is provided. The positiveelectrode active substance is characterized in that the substance has astructure of secondary particles formed by aggregation of primaryparticles, that the average particle diameter of the primary particles(D1) is 0.9 μm or less, and that the average particle diameter of theprimary particles (D1) and the standard deviation (σ) of the averageparticle diameter of the primary particles (D1) meet the relationship ofD1/σ²≧24.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1A is a cross-sectional view schematically illustrating oneembodiment of a core-shell type positive electrode material.

FIG. 1B is a cross-sectional view schematically illustrating anotherembodiment of a core-shell type positive electrode material.

FIG. 2 is a cross-sectional view schematically illustrating the basicstructure of a non-aqueous electrolyte lithium ion secondary battery asone embodiment of the non-aqueous electrolyte lithium ion secondarybattery, in which the non-aqueous electrolyte lithium ion secondarybattery is flat type (stack type) and not a bipolar type.

FIG. 3 is a perspective view illustrating the appearance of a flatlithium ion secondary battery as a representative embodiment of asecondary battery.

DESCRIPTION OF EMBODIMENTS

According to one aspect of the present invention, there is provided apositive electrode active substance for a non-aqueous electrolytesecondary battery comprising a composite oxide containing lithium andnickel having a structure of secondary particles formed by aggregationof primary particles, the average particle diameter of the primaryparticles (D1) is 0.9 μm or less, and the average particle diameter ofthe primary particles (D1) and the standard deviation (σ) of the averageparticle diameter of the primary particles (D1) meet the relationship ofD1/σ²≧24. According to the positive electrode active substance for anon-aqueous electrolyte secondary battery of this aspect, as the averageparticle diameter of the primary particles (D1) is small, thedisplacement amount involved with shrinkage and expansion of activesubstance particles can be kept at low level in the first place.Furthermore, since the average particle diameter of the primaryparticles (D1) and the standard deviation (σ) of the average particlediameter of the primary particles (D1) meet a predeterminedrelationship, variation of the D1 can be suppressed. As a result,miniaturization (cracking) of the secondary particles by breakage ofcrystal structure caused by shrinkage and expansion of active substancecan be suppressed. Consequently, a non-aqueous electrolyte secondarybattery which exhibits a little decrease in capacity when the battery isused for a long period of time and has excellent cycle characteristicscan be provided.

Herein, in the composite oxide containing lithium and nickel, shrinkageand expansion of the composite oxide occur in conjunction withdesorption and insertion of lithium ions when charging and dischargingis performed according to desorption and insertion of lithium ions asdescribed above. As such, there has been a problem in that a greatdecrease in capacity occurs in accordance with repeated charge anddischarge cycles as caused by a factor such as the collapse of thecrystal structure or the like, and a decrease in capacity (decrease incycle characteristics) becomes significant when the battery is used fora long period of time.

Such decrease in cycle characteristics becomes more significant in abattery with layered structure, in particular, a battery installed in anautomobile. Since the battery with layered structure, in particular, abattery installed in an automobile, has a large size unlike a batterygenerally used for a mobile phone or a mobile personal computer, thereis a concern regarding an occurrence of huge temperature differencebetween inside and outside thereof. In a battery with layered structure,the inside of the battery in a layered direction is most prone totemperature increase and it is believed that the temperature thereofdecreases toward the end part due to heat discharge through an outercase. The positive electrode material having a layered rock saltstructure such as a lithium-nickel composite oxide has temperaturedependency of the reaction so that the crystal structure is easilycollapsed in accordance with temperature increase. In this regard, it isbelieved that, in accordance with easy insertion and desorption oflithium ions according to temperature increase, frequency of theshrinkage and expansion of a composite oxide is increased. Namely, asthe temperature unevenness easily occurs in a layered direction, theunevenness in a degree of expansion and shrinkage of a positiveelectrode material also occurs in a layered type battery. When a batteryis used for a long period of time, peeling of particles may easily occurin an area with high temperature load due to shrinkage and expansion ofthe material of a positive electrode active substance. Accordingly, itis believed that a decrease in battery capacity is yielded.

Furthermore, when such a composite oxide is applied to a non-aqueouselectrolyte secondary battery, in particular, a battery installed in anautomobile, significantly longer service life of the secondary batteryis required as compared with the case of the application for electricand mobile electronic devices of a related art. For use in electric andmobile electronic devices of a related art, for example, about 500cycles may be sufficient to the most. However, for a battery installedin an automobile, it is necessary to maintain capacity at certain levelor above even at a cycle number of 1000 to 1500 cycles. Until now, therehave been no enough studies made for a lithium nickel-based compositeoxide which can endure such long-term cycle.

In addition, when the non-aqueous electrolyte secondary battery is usedas a power source of an automobile or the like, it is required to have ahigh volume energy density to further increase a cruising distance.

While keeping in mind the battery for an automobile which is involvedwith such strict requirements, the inventors of the present inventionconducted studies on a lithium nickel-based composite oxide that can beused for a secondary battery with high volume energy density withimproved cycle characteristics.

As a result, the inventors of the present invention found that apositive electrode active substance with excellent cycle characteristicscan be provided while suppressing a decrease in volume energy density bycontrolling the value of the average particle diameter of the primaryparticles (D1) and the relationship between the average particlediameter of the primary particles (D1) and the standard deviation (σ) ofthe average particle diameter of the primary particles (D1) in aspecific range in a lithium nickel-based composite oxide having astructure of secondary particles formed by aggregation of primaryparticles.

The positive electrode active substance according to this aspect is notspecifically limited in terms of the composition as long as it comprisesa composite oxide containing lithium and nickel. Representative examplesof the composite oxide containing lithium and nickel include a lithiumnickel composite oxide (LiNiO₂). However, a composite oxide in whichpart of the nickel atoms of a the lithium nickel composite oxide isreplaced with another metal atom is more preferable. As a preferableexample, a lithium-nickel-manganese-cobalt composite oxide (hereinbelow,also simply referred to as “NMC composite oxide”) has a layered crystalstructure in which a lithium atom layer and a transition metal (Mn, Ni,and Co are arranged with regularity) atom layer are alternately stackedvia an oxygen atom layer, one Li atom is included per atom of transitionmetal M and extractable Li amount is twice the amount of spinel lithiummanganese oxide, that is, as the supply power is two times higher, itcan have high capacity. In addition, as having higher heat stabilitycompared to LiNiO₂, it is particularly advantageous among the nickelcomposite oxides that are used as a positive electrode active substance.

As described herein, the NMC composite oxide includes a composite oxidein which part of transition metal elements are replaced with anothermetal element. In that case, examples of another element include Ti, Zr,Nb, W, P, Al, Mg, V, Ca, Sr, Cr, Fe, B, Ga, In, Si, Mo, Y, Sn, V, Cu,Ag, and Zn. Preferably, it is Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, orCr. More preferably, it is Ti, Zr, P, Al, Mg, or Cr. From the viewpointof improving the cycle characteristics, it is even more preferably Ti,Zr, Al, Mg, or Cr.

By having high theoretical discharge capacity, the NMC composite oxidepreferably has a composition represented by General Formula (1):Li_(a)Ni_(b)Mn_(c)Co_(d)M_(x)O₂ (with the proviso that, in the formula,a, b, c, d, and x satisfy 0.9≦a≦1.2, 0<b<1, 0<c≦0.5, 0<d≦0.5, 0≦x≦0.3,and b+c+d=1. M represents at least one element selected from Ti, Zr, Nb,W, P, Al, Mg, V, Ca, Sr, and Cr). Herein, a represents the atomic ratioof Li, b represents the atomic ratio of Ni, c represents the atomicratio of Mn, d represents the atomic ratio of Co, and x represents theatomic ratio of M. From the viewpoint of the cycle characteristics, itis preferable that 0.4≦b≦0.6 in the General Formula (1). Meanwhile,composition of each element can be measured by induction coupled plasma(ICP) spectroscopy.

In general, from the viewpoint of improving purity and improvingelectron conductivity of a material, nickel (Ni), cobalt (Co) andmanganese (Mn) are known to contribute to capacity and outputcharacteristics. Ti or the like replaces part of transition metal in acrystal lattice. From the viewpoint of the cycle characteristics, it ispreferable that part of transition element are replaced by another metalelement, and it is preferable that 0<x≦0.3 in the General Formula (1),in particular. It is believed that the crystal structure is stabilizedby dissolving at least one selected from the group consisting of Ti, Zr,Nb, W, P, Al, Mg, V, Ca, Sr and Cr so that decrease in capacity of abattery is prevented even after repeated charge and discharge, and thus,excellent cycle characteristics can be achieved.

With regard to the NMC composite oxide, the inventors of the presentinvention found that the influence of deformation and cracking of acomposite oxide during charge and discharge described above becomeshigher if the metal composition of nickel, manganese and cobalt isheterogeneous like LiNi_(0.5)Mn_(0.3)Co_(0.2)O₂. This is believedbecause, as the metal composition is heterogeneous, deformation iscaused in stress applied to the inside of a particle during expansionand shrinkage so that cracks are more easily generated in the compositeoxide. Thus, when comparison is made with a composite oxide having arich Ni abundance ratio (for example, LiNi_(0.8)Mn_(0.1)Co_(0.1)O₂) or acomposite oxide with a homogenous abundance ratio of Ni, Mn and Co (forexample, LiNi_(0.3)Mn_(0.3)Co_(0.3)O₂), more significant decrease inlong-term cycle characteristics is yielded. By having the structureaccording to this aspect, it was found that the cycle characteristicsare surprisingly improved even for a composite oxide having aheterogeneous metal composition like LiNi_(0.5)Mn_(0.3)Co_(0.2)O₂.

Thus, the positive electrode active substance with a composite oxide inwhich b, c, and d in the General Formula (1) satisfy 0.44≦b≦0.51,0.27≦c≦0.31, and 0.19≦d≦0.26 is preferable in that the effect of thepresent invention is obtained at significant level.

The positive electrode active substance according to this aspect has astructure of secondary particles formed by aggregation of primaryparticles. In addition, the average particle diameter of the primaryparticles (D1) is 0.9 μm or less. By having such structure, adisplacement amount of shrinkage and expansion of active substanceparticles can be kept at low level. Furthermore, the average particlediameter of the primary particles (D1) and the standard deviation (s) ofthe average particle diameter of the primary particles (D1) meet therelationship of D1/σ²≧24. As the D1 and the σ meet such a relationship,variation of the D1 can be suppressed. As a result, miniaturization(cracking) of the secondary particles by breakage of crystal structurecaused by shrinkage and expansion of active substance can be suppressed.Consequently, it is speculated that, by having a little decrease incapacity even when the battery is used for a long period of time, anon-aqueous electrolyte secondary battery with excellent cyclecharacteristics is provided. However, the technical scope of the presentinvention is not limited by this mechanism.

The average particle diameter of the primary particles (D1) ispreferably 0.20 to 0.6 μm, and more preferably 0.25 to 0.5 μm. Inaddition, the average particle diameter of the secondary particles (D2)is preferably 5 to 20 μm, and more preferably 5 to 15 μm. In addition,it is preferable that the ratio value thereof (D2/D1) is higher than 11,it is more preferably 15 to 50, and further preferably 25 to 40.Meanwhile, the primary particles forming the lithium nickel-basedcomposite oxide generally have a crystal structure of hexagonal crystalpackage with layered structure. The largeness of the diameter ofcrystallite is related to the largeness of D1. As described herein“crystallite” indicates the largest group which can be determined as amonocrystal, and it can be measured by the method of refining structureparameters of a crystal from diffraction intensity that is obtained bypowder X ray diffraction measurement or the like. The specific value ofthe crystallite diameter is, although not particularly limited,preferably 1 μm or less, more preferably 0.55 μm or less, and even morepreferably 0.4 μm or less. By having such a structure, the displacementamount involved with shrinkage and expansion of an active substance canbe further reduced and an occurrence of micronization (cracking) of thesecondary particles accompanying repetition of charge and discharge isinhibited, which can further contribute to improvement of the cyclecharacteristics. Meanwhile, the lower limit of the diameter of thecrystallite is, although not particularly limited, generally 0.02 μm ormore. In the present specification, the values measured by the methoddescribed in the following Examples are used as values of D1, D2 and thediameter of a crystal of the lithium nickel-based composite oxide.

The tap density of the positive electrode active substance of thisaspect is preferably 2.0 g/cm³ or more, more preferably 2.3 g/cm³ ormore, and even more preferably 2.4 to 2.9 g/cm³. By having such astructure, high density of the primary particles forming the secondaryparticles of the positive electrode active substance is sufficientlyensured, and thus the effect of improving the cycle characteristics canbe maintained.

In addition, the BET specific surface area of the positive electrodeactive substance of this aspect is preferably 0.1 to 1.0 m²/g, morepreferably 0.3 to 1.0 m²/g, and particularly preferably 0.3 to 0.7 m²/g.As the specific surface area of the active substance is within thisrange, the reaction area of the active substance is ensured so that theinternal resistance of a battery is lowered. As a result, an occurrenceof polarization can be suppressed at minimum level at the time of anelectrode reaction.

Furthermore, in the positive electrode active substance of this aspect,the diffraction peak of a (104) surface and the diffraction peak of a(003) surface which are obtained by powder X ray diffraction measurementhave a diffraction peak intensity ratio ((003)/(104)) of preferably 1.28or more and more preferably 1.35 to 2.1. Furthermore, the diffractionpeak integrated intensity ratio ((003)/(104)) is preferably 1.05 ormore, more preferably 1.08 or more, and even more preferably 1.10 to1.45. Those requirements are preferred due to the following reasons.Specifically, the lithium nickel-based composite oxide has a layeredrock salt structure in which Li⁺ layer and Ni³⁺ layer are presentbetween oxygen layers. However, as Ni³⁺ is easily reduced to Ni²⁺ andthe ionic radius of Ni²⁺ (0.83 Å) is substantially equal to the ionicradius of Li⁺ (0.90 Å), it is easy for Ni²⁺ to be incorporated into aLi⁺ defect site which is generated during synthesis of the activesubstance. Once Ni²⁺ is incorporated into the Li⁺ site, anelectrochemically unstable structure is formed locally, and alsodiffusion of Li⁺ is inhibited. For such reasons, when an activesubstance with low crystallinity is used, there is a possibility thatthe battery charge and discharge capacity is lowered or durability isimpaired. Thus, as an indicator of this crystallinity, theaforementioned requirements are employed. Herein, as a method forquantifying the crystallinity, the diffraction peak intensity ratio of a(003) surface to a (104) surface and the integrated intensity ratio ofdiffraction peak, based on crystal structure analysis using X raydiffraction as described above, were used. When these parameters satisfythe above requirements, there are fewer defects within a crystal so thata decrease in battery charge and discharge capacity or impairment ofdurability can be suppressed. Meanwhile, the parameters of crystallinitycan be controlled based on a raw material, a composition, conditions forcalcination, or the like.

With the positive electrode active substance of this aspect, adeformation of a structure which is caused by expansion and shrinkageaccompanying a charge and discharge cycle can be inhibited, and thus itis believed that peeling of particles caused by expansion and shrinkagein the area with high temperature load can be suppressed. As such, evenfor a battery which needs to be used for a long period of time as alayered-structure type battery for an automobile, a decrease in capacitycaused by use for a long period of time is inhibited.

The lithium nickel-based composite oxide such as the NMC composite oxideaccording to this aspect can be produced by selecting various knownmethods such as a co-precipitation method and a spray drying method.From the viewpoint of having easy production of the composite oxideaccording to this aspect, a co-precipitation method is preferably used.Specifically, with regard to a method for synthesizing the NMC compositeoxide, production can be made by, for example, a method described in JP2011-105588 A (corresponding to US 2013/045421 A which is entirelyincorporated herein by reference) in which a nickel-cobalt-manganesecomposite oxide is produced by the co-precipitation method and thenickel-cobalt-manganese composite oxide is admixed with a lithiumcompound followed by calcination. Specific descriptions are givenhereinbelow.

Raw material compounds of a composite oxide, for example, a Ni compound,a Mn compound, or a Co compound, are dissolved in a suitable solventsuch as water so as to have a desired composition of an active substancematerial. Examples of the Ni compound, the Mn compound and the Cocompound include sulfate, nitrate, carbonate, acetate, oxalate, oxide,hydroxide, and halide of the metal element. Specific examples of the Nicompound, the Mn compound and the Co compound include nickel sulfate,cobalt sulfate, manganese sulfate, nickel acetate, cobalt acetate, andmanganese acetate, but not limited thereto. During the process, ifnecessary, in order to have a desired composition of an activesubstance, a compound containing at least one metal element such as Ti,Zr, Nb, W, P, Al, Mg, V, Ca, Sr or Cr as a metal element for replacingpart of the layered lithium metal composite oxide which forms the activesubstance may be further incorporated.

A co-precipitation reaction can be performed by neutralization andprecipitation reactions using the above raw material compounds and analkali solution. Accordingly, metal composite hydroxide or metalcomposite carbonate containing the metal included in the above rawmaterial compounds can be obtained. Examples of the alkali solutionwhich can be used include an aqueous solution of sodium hydroxide,potassium hydroxide, sodium carbonate, or ammonia. For theneutralization reaction, it is preferable to use sodium hydroxide,sodium carbonate, or a mixture solution thereof. In addition, it ispreferable to use an aqueous ammonia solution or ammonia salt for acomplex reaction.

The addition amount of the alkali solution used for neutralizationreaction is sufficient to have the equivalent ratio of 1.0 to componentsto be neutralized which are contained in the whole metal salts. However,for having pH control, it is preferably added together with an excessalkali amount.

The aqueous ammonia solution or ammonia salt used for a complex reactionis preferably added such that the ammonia concentration in the reactionsolution is in a range of 0.01 to 2.00 mol/l. The pH of the reactionsolution is preferably controlled in a range of 10.0 to 13.0. Thereaction temperature is preferably 30° C. or higher, and more preferably30 to 60° C.

The composite hydroxide obtained by co-precipitation reaction is thenpreferably filtered by suction, washed with water, and dried. Meanwhile,by controlling the conditions for performing the co-precipitationreaction (for example, stirring time and alkali concentration), particlediameter of the composite hydroxide can be controlled, and it has aninfluence on the average particle diameter of the secondary particles(D2) of a positive electrode active substance which is finally obtained.

Subsequently, by mixing and calcining nickel-cobalt-manganese compositehydroxide with a lithium compound, the lithium-nickel-manganese-cobaltcomposite oxide can be obtained. Examples of the Li compound includelithium hydroxide or a hydrate thereof, lithium peroxide, lithiumnitrate and lithium carbonate.

The calcination, treatment can be performed by one step, but it ispreferably performed by two steps (temporary calcination and maincalcination). According to two-step calcination, a composite oxide canbe obtained efficiently. The conditions for temporary calcination arenot particularly limited, and they may vary depending on the lithium rawmaterial or the like, and thus cannot be unambiguously defined. Here, asthe factors for controlling D1 and σ (and also Dl/σ²) and crystallitediameter in particular, calcination temperature and calcination time forcalcination (temporary calcination and main calcination in the case of atwo-step calcination.) are particularly important. By making a controlof them based on the tendency described below, D1 and σ (and also D1/σ²)and the crystallite diameter can be controlled. Namely, D1, σ andcrystallite particle diameter are increased by having longer calcinationtime, Dl,σ and crystallite particle diameter are also increased byincreasing the calcination temperature. Meanwhile, the temperatureincrease rate is preferably 1 to 20° C/minute from room temperature.Furthermore, the atmosphere is preferably either air or oxygenatmosphere. Here, when the NMC composite oxide is synthesized by usinglithium carbonate as the Li raw material, temperature for temporarycalcination is preferably 500 to 900° C., more preferably 600 to 800°C., and even more preferably 650 to 750° C. Furthermore, time fortemporary calcination is preferably 0.5 to 10 hours and more preferably4 to 6 hours. Meanwhile, as for the conditions for main calcination, thetemperature increase rate is preferably 1 to 20° C/minute from roomtemperature, although it is not particularly limited thereto.Furthermore, the atmosphere is preferably either air or oxygenatmosphere. Here, when the NMC composite oxide is synthesized by usinglithium carbonate as the Li raw material, temperature for calcination ispreferably 800 to 1200° C., more preferably 850 to 1100° C., and evenmore preferably 900 to 1050° C. Furthermore, time for calcination ispreferably 1 to 20 hours and more preferably 8 to 12 hours.

When a tiny amount of a metal element for replacing part of the layeredlithium metal composite oxide forming an active substance material isadded as needed, any means such as mixing it in advance with nickel,cobalt, manganate salt, adding it simultaneously with nickel, cobalt,lithium manganate salt, adding it to a reaction solution during thereaction, or adding it to the nickel-cobalt-manganese composite oxidewith a Li compound can be employed.

The composite oxide of the present invention can be produced by suitablycontrolling the reaction conditions such as pH of a reaction solution,reaction temperature, reaction concentration, addition rate, and timefor stirring.

According to one embodiment of the positive electrode active substanceof this aspect, a positive electrode material for a non-aqueouselectrolyte secondary battery of core-shell type, which has a core partcontaining the positive electrode active substance according to theaforementioned first aspect and a shell part containing alithium-containing composite oxide that is different from the positiveelectrode active substance, is provided.

FIG. 1A is a schematic cross-sectional view of an active substanceparticle as one embodiment of the core-shell type positive electrodematerial, in which the inside of the particles has a structure of thecore-shell type structure due to different active substance materials.In FIG. 1A and FIG. 1B, 1 indicates a shell part of a positive electrodematerial, 2 indicates a core part of a positive electrode material, and3 indicates a positive electrode material. With this core-shellstructure, cycle characteristics of a non-aqueous electrolyte secondarybattery are further improved. According to the study by the presentinventors, it was verified that only the particle surface layer part hasa reduction in Ni valency, as a result of analyzing the NMC compositeoxide particles after cycle durability test. Based on this, the presetinventors made a presumption that, as Ni on particle surface layer partis inactivated, it actually may not contribute to charge and discharge.Subsequently, it was assumed that further improvement of the cyclecharacteristics can be obtained by having the NMC composite oxide withlow Ni concentration or a material other than Ni on a topical area proneto deterioration, and it was consequently proven.

The core part can be a single layer (monolayer) or has a structure oftwo or more layers. Examples of the embodiment in which the core part iscomposed of two or more layers include (1) a structure in which plurallayers are stacked, from the surface to the center of the core part, inconcentric circle shape and (2) a structure in which content variescontinuously from the surface to the center of the core part. In thosecases, by modifying the material for each layer or modifying the mixingratio of two or more active substance materials, a change can be madesuch that performances such as capacity or output increase or decreasefrom the surface to the center of the core part (functional gradient).Furthermore, the present invention may include production by agranulation technique using two or more materials. For example, (3) asea-island structure in which different materials are sprinkled in anisland shape within a matrix material is also possible. It can be also(4) a structure in which different materials are present on a hemispherepart of the core particles. It can be also (5) a secondary particle(aggregated) structure in which groups of microparticles consisting ofdifferent materials are put together and granulated by solidification.It can be also a structure in which the above (1) to (5) are suitablycombined. From the viewpoint of the easy production, and lowering thenumber of kinds of material and production steps (lowering the cost formaterial and production), it is preferable to have a single layer(monolayer) structure.

The shape of the core part may be, although not particularly limited, asphere shape, a cubic shape, a rectangle shape, an ellipsoid shape, aneedle shape, a plate shape, a prism shape, a column shape, and anamorphous shape. It is preferably a sphere shape or an ellipsoid shape.

The shell part may be formed on an outer side (outer layer) of the corepart, and it may be a single layer (monolayer) or has a structure of twoor more layers.

Furthermore, the shell part is not limited to the form in which itcovers the entire core part, and it may coat only part of the core part(a composite oxide of a shell part is sprinkled on a surface of acomposite oxide of the core part and part of the surface of the corepart may remain exposed).

Furthermore, the shell part may be present in a layered form so as tocoat the entire surface of the core part (see, FIG. 1A), or it may bepresent to cover (impregnate) the entire surface of the core part byusing plural microparticles (powder) (see, FIG. 1B).

Examples of the embodiment of preparing the shell part to have two ormore layers include the structures (1) to (5) that are described abovefor the core part.

The lithium composite oxide contained in the shell part is notparticularly limited as long as it is a lithium-containing compositeoxide which is different from the aforementioned positive electrodeactive substance according to the first aspect of the present invention.Specific examples thereof include lithium manganate of a spinelstructure such as LiMn₂O₄, lithium manganate such as LiMnO₂ and Li₂MnO₃,a lithium nickel-based composite oxide having a composition differentfrom the positive electrode active substance according to theaforementioned first aspect (for example, the NMC composite oxide),lithium cobalt acid such as LiCoO₂, lithium nickel acid such as LiNiO₂,lithium iron oxide such as LiFeO₂, and lithium iron phosphate such asLiFePO₄. Among them, from the viewpoint of the cycle characteristics,the lithium nickel-based composite oxide having a composition differentfrom the positive electrode active substance according to theaforementioned first aspect (for example, the NMC composite oxide),lithium nickel acid, or a manganese positive electrode active substanceof a spinel type is preferable. More preferably, it is the NMC compositeoxide having a composition different from the positive electrode activesubstance according to the aforementioned first aspect (preferably, itis represented by General Formula (2):Li_(a′)Ni_(b′)Co_(c′)Mn_(d′)M_(x′)O₂ (with the proviso that, in GeneralFormula (2), a′, b′, c′, d′, and x′ satisfy 0.9≦a′≦1.2, 0<b′<1,0<c′≦0.5, 0<d′≦0.5, 0≦x′≦0.3, and b+c+d=1. M includes at least oneelement selected from Ti, Zr, Nb, W, P, Al, Mg, V, Ca, and Sr)).

Furthermore, the positive electrode active substance contained in thecore part is preferably a composite oxide in which b, c and d of theGeneral Formula (1) are as follows: 0.44≦b≦0.51, 0.27≦c≦0.31,0.19≦d≦0.26, and the composite oxide contained in the shell part ispreferably a lithium nickel-based composite oxide having a compositiondifferent from the positive electrode active substance according to theaforementioned first aspect, and more preferably the NMC composite oxidehaving a composition different from the positive electrode activesubstance of the aforementioned first aspect.

The composite oxide contained in the shell part maybe a single layer(monolayer) or has a structure of two or more layers. When the shellpart is composed of two or more layers, a single type of an activesubstance material may be used for each layer, or two or more materialsmay be mixed and used for each layer.

In a positive electrode material having this core-shell type structure,the shell part is preferably 1 to 30% by weight, and more preferably 1to 15% by weight relative to 100% by weight of the core part. Meanwhile,the positive electrode material having a core-shell type structure canbe produced according to a method described in JP 2007-213866 A.

According to still another aspect of the present invention, a positiveelectrode material obtained by having the positive electrode activesubstance according to the aforementioned first aspect of the presentinvention and a spinel type manganese positive electrode activesubstance in a mixed state is provided. The present inventors found thatthe NMC composite oxide has a problem in that it has a great voltagelowering during high output discharge at low temperature, for example,insufficient output of an automobile in a cold region. In thisconnection, they found that, by mixing the NMC composite oxide with aspinel type manganese positive electrode active substance, voltagelowering during high output discharge at low temperature is reduced andalso insufficient output of an automobile in a cold region is improved.

The mixing weight ratio between the positive electrode active substanceaccording to the aforementioned first aspect and the spinel typemanganese positive electrode active substance is, from the viewpoint ofthe cycle characteristics, preferably as follows: positive electrodeactive substance according to the aforementioned first aspect:spineltype manganese positive electrode active substance=50:50 to 90:10. Fromthe viewpoint of the balance in capacity, service life, and heatstability, it is more preferably 70:30 to 90:10.

According to still another aspect of the present invention, a positiveelectrode obtained by forming, on a surface of a positive electrodecurrent collector, a layer of a positive electrode active substancecontaining at least one selected from the group consisting of thepositive electrode active substance according to the aforementionedfirst aspect of the present invention, a positive electrode material ofa core-shell type, and a positive electrode material resulting frommixing of the positive electrode active substance according to theaforementioned first aspect and the spinel type manganese positiveelectrode active substance is provided.

Meanwhile, it is needless to say that the positive electrode may containother positive electrode active substance which plays a role as anactive substance. However, the total content of the material selectedfrom the group consisting of the positive electrode active substanceaccording to the aforementioned first aspect of the present invention, apositive electrode material of a core-shell type, and a positiveelectrode material resulting from mixing of the positive electrodeactive substance according to the aforementioned first aspect and thespinel type manganese positive electrode active substance is preferably80 to 100% by weight, more preferably 95 to 100% by weight, and evenmore preferably 100% by weight relative to 100% by weight of thematerial which can function as a positive electrode active substance tobe contained in the positive electrode active substance layer.

If necessary, the positive electrode active substance layer furthercontains other additives such as a conductive aid, a binder, anelectrolyte (for example, polymer matrix, ion conductive polymer, andelectrolyte solution), and lithium salt for enhancing ion conductivityin addition to the active substance.

The content of the material capable of functioning as a positiveelectrode active substance is preferably 85 to 99.5% by weight in thepositive electrode active substance layer.

(Binder)

A binder used for the positive electrode active substance layer is notparticularly limited and the following materials can be mentioned;thermoplastic polymers such as polyethylene, polypropylene, polyethyleneterephthalate (PET), polyether nitrile, polyacrylonitrile, polyimide,polyamide, cellulose, carboxymethyl cellulose (CMC) and a salt thereof,an ethylene-vinyl acetate copolymer, polyvinylidene chloride,styrene-butadiene rubber (SBR), isoprene rubber, butadiene rubber,ethylene-propylene rubber, an ethylene-propylene-diene copolymer, astyrene-butadiene-styrene block copolymer and a hydrogen-added productthereof, and a styrene-isoprene-styrene block copolymer and ahydrogen-added product thereof, fluorine resins such as polyvinylidenefluoride (PVdF), polytetrafluoroethylene (PTFE), atetrafluoroethylene-hexafluoropropylene copolymer (FEP), atetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), anethylene-tetrafluoroethylene copolymer (ETFE),polychlorotrifluoroethylene (PCTFE), an ethylene-chlorotrifluoroethylenecopolymer (ECTFE), and polyvinyl fluoride (PVF), vinylidenefluoride-based fluorine rubber such as vinylidenefluoride-hexafluoropropylene-based fluorine rubber (VDF-HFP-basedfluorine rubber), vinylidenefluoride-hexafluoropropylene-tetrafluoroethylene-based fluorine rubber(VDF-HFP-TFE-based fluorine rubber), vinylidenefluoride-pentafluoropropylene-based fluorine rubber (VDF-PFP-basedfluorine rubber), vinylidenefluoride-pentafluoropropylene-tetrafluoroethylene-based fluorine rubber(VDF-PFP-TFE-based fluorine rubber), vinylidene fluoride-perfluoromethylvinyl ether-tetrafluoroethylene-based rubber (VDF-PFMVE-TFE-basedfluorine rubber), and vinylidene fluoride-chlorotrifluoroethylenefluorine-based rubber (VDF-CTFE-based fluorine rubber), an epoxy resin,and the like. These binders may be each used singly, or two or morethereof may be used in combination.

The amount of the binder contained in the positive electrode activesubstance layer is not particularly limited as long as the binder canbind the active substance. The amount of binder is preferably 0.5 to 15%by weight, more preferably 1 to 10% by weight with respect to the activesubstance layer.

If necessary, the positive electrode active substance layer furthercontains other additives such as a conductive aid, an electrolyte (forexample, polymer matrix, ion conductive polymer, and electrolytesolution), and lithium salt for enhancing ion conductivity.

The conductive aid means an additive which is blended in order toenhance the conductivity of the positive electrode active substancelayer or negative electrode active substance layer. Examples of theconductive aid include carbon materials such as carbon black includingketjen black and acetylene black; graphite; and carbon fiber. When theactive substance layer contains a conductive aid, an electron network inthe inside of the active substance layer is formed effectively, and itcan contribute to improvement of the output characteristics of abattery.

Examples of the electrolyte salt (lithium salt) include Li(C₂F₅SO₂)₂N,LiPF₆, LiBF₄, LiClO₄, LiASF₆, and LiCF₃SO₃.

Examples of the ion conductive polymer include polyethylene oxide(PEO)-based and polypropylene oxide (PPO)-based polymer.

A blending ratio of the components that are contained in the positiveelectrode active substance layer and negative electrode active substancelayer described below is not particularly limited. The blending ratiocan be adjusted by suitably referring to the already-known knowledgeabout a lithium ion secondary battery. The thickness of each activesubstance layer is not particularly limited either, and reference can bemade to the already-known knowledge about a battery. For example, thethickness of each active substance layer is about 2 to 100 μm.

According to still another embodiment of the present invention, anon-aqueous electrolyte secondary battery having a power generatingelement including the aforementioned positive electrode, a negativeelectrode obtained by forming a negative electrode active substancelayer on a surface of a negative electrode current collector, and aseparator can be provided.

Next, a description will be made of a non-aqueous electrolyte lithiumion secondary battery as a preferred embodiment of the non-aqueouselectrolyte secondary battery, but it is not limited thereto. Meanwhile,the same elements are given with the same symbols for the descriptionsof the drawings, and overlapped descriptions are omitted. Further, notethat dimensional ratios in the drawings are exaggerated for the sake ofdescription, and are different from actual ratios in some cases.

FIG. 2 is a cross-sectional view schematically illustrating the basicconstitution of a non-aqueous electrolyte lithium ion secondary batterywhich is not a bipolar type of a flat type (stack type) (hereinbelow, itis also simply referred to as a “stack type battery”). As illustrated inFIG. 2, the stack type battery 10 according to this embodiment has astructure in which a power generating element 21 with a substantiallyrectangular shape, in which a charge and discharge reaction actuallyoccurs, is sealed inside of a battery outer casing material 29 as anouter casing body. Herein, the power generating element 21 has aconstitution in which a positive electrode, the separator 17, and anegative electrode are stacked. Meanwhile, the separator 17 has anon-aqueous electrolyte (for example, liquid electrolyte) within it. Thepositive electrode has a structure in which the positive electrodeactive substance layer 13 is disposed on both surfaces of the positiveelectrode current collector 11. The negative electrode has a structurein which the negative electrode active substance layer 15 is disposed onboth surfaces of the negative electrode current collector 12.Specifically, one positive electrode active substance layer 13 and theneighboring negative electrode active substance layer 15 are disposed toface each other via the separator 17, and the negative electrode, theelectrolyte layer and the positive electrode are stacked in this order.Accordingly, the neighboring positive electrode, electrolyte layer andnegative electrode form one single battery layer 19. As such, it can bealso said that, as plural single battery layers 19 are stacked, thestack type battery 10 illustrated in FIG. 2 has a constitution in whichelectrically parallel connection is made among them.

Meanwhile, on the outermost layer positive electrode current collectorwhich is present on both outermost layers of the power generatingelement 21, the positive electrode active substance layer 13 is disposedonly on a single surface. However, an active substance layer may beformed on both surfaces. Namely, not only a current collector exclusivefor an outermost layer in which an active substance layer is formed on asingle surface can be achieved but also a current collector having anactive substance layer on both surfaces can be directly used as acurrent collector of an outermost layer. Furthermore, by reversing thearrangement of the positive electrode and negative electrode of FIG. 2,it is also possible that the outer most layer negative electrode currentcollector is disposed on both outermost layers of the power generatingelement 21 and a negative electrode active substance layer is disposedon a single surface or both surfaces of the same outermost layernegative electrode current collector.

The positive electrode current collector 11 and negative electrodecurrent collector 12 have a structure in which each of the positiveelectrode current collecting plate (tab) 25 and negative electrodecurrent collecting plate (tab) 27, which conductively communicate witheach electrode (positive electrode and negative electrode), is attachedand inserted to the end part of the battery outer casing material 29 soas to be led to the outside of the battery outer casing material 29. Ifnecessary, each of the positive electrode current collecting plate 25and negative electrode current collecting plate 27 can be attached, viaa positive electrode lead and negative electrode lead (not illustrated),to the positive electrode current collector 11 and negative electrodecurrent collector 12 of each electrode by ultrasonic welding orresistance welding.

Meanwhile, although a stack type battery is illustrated in FIG. 2instead of a bipolar type of a flat type (stack type), it can be also abipolar type battery containing a bipolar type electrode which has apositive electrode active substance layer electrically bound to onesurface of a current collector and a negative electrode active substancelayer electrically bound to the opposite surface of the currentcollector. In that case, one current collector plays both roles of apositive electrode current collector and a negative electrode currentcollector.

Hereinbelow, each member is described in more detail.

[Negative Electrode Active Substance Layer]

The negative electrode active substance layer contains an activesubstance, and if necessary, further contains other additives such as aconductive aid, a binder, an electrolyte (for example, polymer matrix,ion conductive polymer, and electrolyte solution), and lithium salt forenhancing ion conductivity. The other additives such as a conductiveaid, a binder, an electrolyte (for example, polymer matrix, ionconductive polymer, and electrolyte solution), and lithium salt forenhancing ion conductivity are the same as those described above for thepositive electrode active substance layer.

The negative electrode active substance layer preferably contains atleast an aqueous binder. The aqueous binder has a high binding property.Further, since water as a raw material is easily available and also onlywater vapor is generated during drying, there is an advantage that theinvestment on facilities of a production line can be greatly reduced andan environmental load can be reduced.

The aqueous binder indicates a binder which has water as a solvent or adispersion medium, and specific examples thereof include a thermoplasticresin, a polymer with rubber elasticity, a water soluble polymer, and amixture thereof. Herein, the binder which has water as a dispersionmedium includes all expressed as latex or an emulsion, and it indicatesa polymer emulsified in water or suspended in water. Examples thereofinclude a polymer latex obtained by emulsion polymerization in aself-emulsifying system.

Specific examples of the aqueous binder include a styrene polymer(styrene-butadiene rubber, styrene-vinyl acetic acid copolymer,styrene-acryl copolymer or the like), acrylonitrile-butadiene rubber,methacrylic acid, methyl-butadiene rubber, (meth)acrylic polymer(polyethylacrylate, polyothylmethacrylate, polypropylacrylate,polymethylmethacrylate (methacrylic acid methyl rubber),polypropylmethaorylate, polyisopropylacrylate,polyisopropylmethacrylate, polybutylacrylate, polybutylmethacrylate,polyhexylacrylate, polyhexylmethacrylate, polyethylhexylacrylate,polyethylhexylmethacrylate, polylaurylacrylate, polylaurylmethacrylate,or the like) , polytetrafluoroethylene, polyethylene, polypropylene, anethylene-propylene copolymer, polybutadiene, butyl rubber, fluororubber,polyethylene oxide, polyepichlorohydrin, polyphosphagen,polyacrylonitrle, polystyrene, an ethylene-propylene-diene copolymer,polyvinylpyridine, chlorosulfonated polyethylene, a polyester resin, aphenol resin, an epoxy resin; polyvinyl alcohol (average polymerization.degree is preferably 200 to 4000, and more preferably 1000 to 3000, andsaponification degree is preferably 80%; by mol or more, and morepreferably 90% by mol or more) and a modified product thereof (1 to 80%by mol saponified product in a vinyl acetate unit of a copolymer withethylene/vinyl acetate =2/98 to 30/70 (molar ratio), 1 to 50% by molpartially acetalized product of polyvinyl alcohol, or the like) , starchand a modified product (oxidized starch, phosphoric acid esterifiedstarch, cationized starch, or the like), cellulose derivatives(carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose,hydroxyethyl cellulose, and a salt thereof) , polyvinylpyrrolidone,polyacrylic acid (salt), polyethylene gylcol, a copolymer of(meth)acrylamide and/or (meth) acrylic acid salt [(meth)acrylamidepolymer, (meth)acrylamide -(meth) acrylic acid salt copolymer, alkyl(meth) acrylic acid (carbon atom number of 1 to 4) ester-(meth) acrylicacid salt copolymer, or the like] , a styrene-maleic acid saltcopolymer, a mannich modified product of polyacrylamide, a formalincondensation type resin (urea-formalin resin, melamin- formalin resin orthe like) , a polyamidepolyamine or dialkylamine-epichlorohydrincopolymer, polyethyleneimine, casein, soybean protein, syntheticprotein, and a water soluble polymer such as galactan mannanderivatives. The aqueous binder can be used either singly or incombination of two or more types.

From the viewpoint of a binding property, the aqueous binder preferablycontains at least one rubber-based binder selected from a groupconsisting of styrene-butadiene rubber, acrylonitrile-butadiene rubber,methacrylic acid methyl-butadiene rubber, and methacrylic acid methylrubber. Further, from the viewpoint of having a good binding property,the aqueous binder preferably contains styrene-butadiene rubber.

When styrene-butadiene rubber is used as an aqueous binder, theaforementioned water soluble polymer is preferably used in combinationfrom the viewpoint of improving the coating property. Examples of thewater soluble polymer which is preferably used in combination withstyrene-butadiene rubber include polyvinyl alcohol and a modifiedproduct thereof, starch and a modified product thereof, cellulosederivatives (carboxymethyl cellulose, methyl cellulose, hydroxyethylcellulose, and a salt thereof), polyvinylpyrrolidone, polyacrylic acid(salt), and polyethylene glycol. Among them, styrene-butadiene rubberand carboxymethyl cellulose (salt) are preferably combined as a binder.The weight content ratio between styrene-butadiene rubber and a watersoluble polymer is, although not particularly limited, preferably asfollows: styrene-butadiene rubber:water soluble polymer=1:0.1 to 10, andmore preferably 0.5 to 2.

In a binder used for the negative electrode active substance layer, thecontent of the aqueous binder is preferably 80 to 100% by weight,preferably 90 to 100% by weight, and preferably 100% by weight.

Examples of the negative electrode active substance include a carbonmaterial such as graphite, soft carbon, and hard carbon, alithium-transition metal composite oxide (for example, Li₄Ti₅O₁₂), ametal material, and a lithium alloy-based negative electrode material.If necessary, two or more kinds of a negative electrode active substancemay be used in combination. Preferably, from the viewpoint of capacityand output characteristics, a carbon material or a lithium-transitionmetal composite oxide is used as a negative electrode active substance.Meanwhile, it is needless to say that a negative electrode activesubstance other than those described above can be also used.

The average particle diameter of a negative electrode active substanceis, although not particularly limited, preferably 1 to 100 μm, and morepreferably 1 to 20 μm from the viewpoint of having high output.

[Separator (Electrolyte Layer)]

A separator has a function of maintaining an electrolyte to ensurelithium ion conductivity between a positive electrode and a negativeelectrode and also a function of a partition wall between a positiveelectrode and a negative electrode.

Examples of a separator shape include a porous sheet separator or anon-woven separator composed of a polymer or a fiber which absorbs andmaintains the electrolyte.

As a porous sheet separator composed of a polymer or a fiber, amicroporous (microporous membrane) separator can be used, for example.Specific examples of the porous sheet composed of a polymer or a fiberinclude a microporous (microporous membrane) separator which is composedof polyolefin such as polyethylene (PE) and polypropylene (PP); alaminate in which plural of them are laminated (for example, a laminatewith three-layer structure of PP/PE/PP), and a hydrocarbon based resinsuch as polyimide, aramid, or polyfluorovinylydene-hexafluoropropylene(PVdF-HFP), or glass fiber.

The thickness of the microporous (microporous membrane) separator cannotbe uniformly defined as it varies depending on use of application. Forexample, for an application in a secondary battery for operating a motorof an electric vehicle (EV), a hybrid electric vehicle (HEV), and a fuelcell vehicle (FCV), it is preferably 4 to 60 μm as a monolayer or amultilayer. Fine pore diameter of the microporous (microporous membrane)separator is preferably 1 μm or less at most (in general, the porediameter is about several tens of nanometers).

As a non-woven separator, conventionally known ones such as cotton,rayon, acetate, nylon, polyester; polyolefin such as PP and PE;polyimide and aramid are used either singly or as a mixture.Furthermore, the volume density of a non-woven fabric is notparticularly limited as long as sufficient battery characteristics areobtained with an impregnated electrolyte. Furthermore, it is sufficientthat the thickness of the non-woven separator is the same as that of anelectrolyte layer. Preferably, it is 5 to 200 μm. Particularlypreferably, it is 10 to 100 μm.

As described above, the separator also contains an electrolyte. Theelectrolyte is not particularly limited if it can exhibit thosefunctions, and a liquid electrolyte or a gel polymer electrolyte isused. By using a gel polymer electrolyte, a distance between electrodesis stabilized and an occurrence of polarization is suppressed so thatthe durability (cycle characteristics) is improved.

The liquid electrolyte has an activity of a lithium ion carrier. Theliquid electrolyte constituting an electrolyte solution layer has theform in which lithium salt as a supporting salt is dissolved in anorganic solvent as a plasticizer. Examples of the organic solvent whichcan be used include carbonates such as ethylene carbonate (EC),propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate(DEC), and ethylmethyl carbonate. Furthermore, as a lithium salt, thecompound which can be added to an active substance layer of an electrodesuch as Li(CF₃SO₂)₂N, Li(C₂F₅SO₂)₂N, LiPF₆, LiBF₄, LiClO₄, LiAsF₆,LiTaF₆, and LiCF₃SO₃ can be similarly used. The liquid electrolyte mayfurther contain an additive in addition to the components that aredescribed above. Specific examples of the compound include vinylenecarbonate, methylvinylene carbonate, dimethylvinylene carbonate,phenylvinylene carbonate, diphenylvinylene carbonate, ethylvinylenecarbonate, diethylvinylene carbonate, vinylethylene carbonate,1,2-divinylethylene carbonate, 1-methyl-1-vinylethylene carbonate,1-methyl-2-vinylethylene carbonate, 1-ethyl-1-vinylethylene carbonate,1-ethyl-2-vinylethylene carbonate, vinylvinylene carbonate,allylethylene carbonate, vinyloxymethylethylene carbonate,allyloxymethylethylene carbonate, acryloxymethylethylene carbonate,methacryloxymethylethylene carbonate, ethynylethylene carbonate,propargylethylene carbonate, ethynyloxymethylethylene carbonate,propargyloxyethylene carbonate, methylene ethylene carbonate, and1,1-dimethyl-2-methyleneethylene carbonate. Among them, vinylenecarbonate, methylvinylene carbonate, and vinylethylene carbonate arepreferable. Vinylene carbonate and vinylethylene carbonate are morepreferable. Those cyclic carbonate esters may be used either singly orin combination of two or more types.

The gel polymer electrolyte has a constitution that the aforementionedliquid electrolyte is injected to a matrix polymer (host polymer)consisting of an ion conductive polymer. Using a gel polymer electrolyteas an electrolyte is excellent in that the fluidity of an electrolytedisappears and ion conductivity between layers is blocked. Examples ofan ion conductive polymer which is used as a matrix polymer (hostpolymer) include polyethylene oxide (PEO), polypropylene oxide (PPO),polyethylene glycol (PEG), polyacrylronitrile (PAN), polyvinylidenefluoride-hexafluoropropylene (PVdF-HEP), poly(methyl methacrylate (PMMA)and a copolymer thereof.

According to forming of a cross-linked structure, the matrix polymer ofa gel electrolyte can exhibit excellent mechanical strength. For forminga cross-linked structure, it is sufficient to perform a polymerizationtreatment of a polymerizable polymer for forming a polymer electrolyte(for example, PEO and PPO), such as thermal polymerization, UVpolymerization, radiation polymerization, and electron beampolymerization, by using a suitable polymerization initiator.

Furthermore, as a separator, a separator laminated with a heat resistantinsulating layer laminated on a porous substrate (a separator having aheat resistant insulating layer) is preferable. The heat resistantinsulating layer is a ceramic layer containing inorganic particles and abinder. As for the separator having a heat resistant insulating layer,those having high heat resistance, that is, melting point or heatsoftening point of 150° C. or higher, preferably 200° C. or higher, areused. By having a heat resistant insulating layer, internal stress in aseparator which increases under temperature increase is alleviated sothat the effect of inhibiting thermal shrinkage can be obtained. As aresult, an occurrence of a short between electrodes of a battery can beprevented so that a battery configuration not easily allowing aperformance reduction as caused by temperature increase is yielded.Furthermore, by having a heat resistant insulating layer, mechanicalstrength of a separator having a heat resistant insulating layer isimproved so that the separator hardly has a film breaking. Furthermore,because of the effect of inhibiting thermal shrinkage and a high levelof mechanical strength, the separator is hardly curled during theprocess of fabricating a battery.

The inorganic particles in a heat resistant insulating layer contributeto the mechanical strength or the effect of inhibiting thermal shrinkageof a heat resistant insulating layer. The material used as inorganicparticles is not particularly limited. Examples thereof include oxides(SiO₂, Al₂O₃, ZrO₂, TiO₂), hydroxides and nitrides of silicon, aluminum,zirconium and titanium, and a composite thereof. The inorganic particlesmay be derived from mineral resources such as boehmite, zeolite,apatite, kaolin, mullite, spinel, olivine, and mica, or artificiallysynthesized. Furthermore, the inorganic particles may be used eithersingly or in combination of two or more types. From the viewpoint of thecost, it is preferable to use silica (SiO₂) or alumina (Al₂O₃) amongthem. It is more preferable to use alumina (Al₂O₃).

The weight per unit area of heat resistant particles is, although notparticularly limited, preferably 5 to 15 g/m². When it is within thisrange, sufficient ion conductivity is obtained and heat resistantstrength is maintained, and thus desirable.

The binder in a heat resistant insulating layer has a role of adheringinorganic particles or adhering inorganic particles to a porous resinsubstrate layer. With this binder, the heat resistant insulating layeris stably formed and peeling between a porous substrate layer and a heatresistant insulating layer is prevented.

The binder used for a heat resistant insulating layer is notparticularly limited, and examples thereof which can be used include acompound such as carboxymethyl cellulose (CMC), polyacrylronitrile,cellulose, an ethylene-vinyl acetate copolymer, polyvinyl chloride,styrene-butadiene rubber (SBR), isoprene rubber, butadiene rubber,polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE),polyvinyl fluoride (PVF), and methyl acrylate. Among them, carboxymethylcellulose (CMC), methyl acrylate, or polyvinylidene fluoride (PVDF) ispreferably used. Those compounds may be used either singly or incombination of two or more types.

The content of the binder in a heat resistant insulating layer ispreferably 2 to 20% by weight relative to 100% by weight of the heatresistant insulating layer. When the binder content is 2% by weight ormore, the peeling strength between the heat resistant insulating layerand a porous substrate layer can be increased and vibration resistanceof a separator can be enhanced. Meanwhile, when the binder content is20% by weight or less, a gap between inorganic particles is maintainedat an appropriate level so that sufficient lithium ion conductivity canbe ensured.

Regarding the thermal shrinkage rate of a separator having a heatresistant insulating layer, both MD and TD are 10% or less aftermaintaining for 1 hour at conditions of 150° C., 2 gf/cm². By using amaterial with such high heat resistance, shrinkage of a separator can beeffectively prevented even when the internal temperature of a batteryreaches 150° C. due to increased heat generation amount from a positiveelectrode. As a result, an occurrence of a short between electrodes of abattery can be prevented, and thus a battery configuration not easilyallowing performance reduction due to temperature increase is yielded.

[Current Collector]

The material for forming a current collector is not particularlylimited, but metal is preferably used.

Specific examples of the metal include aluminum, nickel, iron,stainless, titanium, copper, and other alloys. In addition to them, aclad material of nickel and aluminum, a clad material of copper andaluminum, or a plating material of a combination of those metals can bepreferably used. It can be also a foil obtained by coating aluminum on ametal surface. Among them, from the viewpoint of electron conductivityor potential for operating a battery, aluminum, stainless, and copperare preferable.

The size of the current collector is determined based on use of abattery. When it is used for a large-size battery which requires highenergy density, for example, a current collector with large area isused. The thickness of the current collector is not particularlylimited, either. The thickness of the current collector is generallyabout 1 to 100 μm.

[Positive Electrode Current Collecting Plate and Negative ElectrodeCurrent Collecting Plate]

The material for forming the current collecting plate (25, 27) is notparticularly limited, and a known highly conductive material which hasbeen conventionally used for a current collecting plate for a lithiumion secondary battery can be used. Preferred examples of the materialfor forming a current collecting plate include metal materials such asaluminum, copper, titanium, nickel, stainless steel (SUS) and an alloythereof. From the viewpoint of light weightiness, resistance tocorrosion, and high conductivity, aluminum and copper are preferable.Aluminum is particularly preferable. Meanwhile, the same material or adifferent material can be used for the positive electrode currentcollecting plate 25 and the negative electrode current collecting plate27.

[Positive Electrode Lead and Negative Electrode Lead]

Further, although it is not illustrated, the current collector 11 andthe current collecting plate (25, 27) can be electrically connected toeach other via a positive electrode lead or a negative electrode lead.The same material used for a lithium ion secondary battery of a relatedart can be also used as a material for forming a positive electrode leadand a negative electrode lead. Meanwhile, a portion led from an outercasing is preferably coated with a heat resistant and insulatingthermally shrunken tube or the like so that it has no influence on aproduct (for example, an automobile component, in particular, anelectronic device or the like) according to electric leak after contactwith neighboring instruments or wirings.

[Battery Outer Casing Body]

As for the battery outer casing body 29, an envelope-shaped casing tocover a power generating element, in which a laminate film includingaluminum is contained, can be used in addition to a known metal cancasing. As for the laminate film, a laminate film with a three-layerstructure formed by laminating PP, aluminum and nylon in order can beused, but not limited thereto. From the viewpoint of having high outputand excellent cooling performance, and of being suitably usable for abattery for a large instrument such as EV or HEV, a laminate film ispreferable. Furthermore, as the group pressure applied from outside to apower generating element can be easily controlled and thus the thicknessof an electrolyte solution layer can be easily controlled to a desiredvalue, an aluminate laminate is more preferred for an outer casing body.

[Cell Size]

FIG. 3 is a perspective view illustrating the appearance of a flatlithium ion secondary battery as a representative embodiment of asecondary battery.

As illustrated in FIG. 3, the flat lithium ion secondary battery 50 hasa flat and rectangular shape, and from both sides, the positiveelectrode tab 58 and the negative electrode tab 59 are drawn to extractelectric power. The power generating element 57 is covered by thebattery outer casing material 52 of the lithium ion secondary battery 50with its periphery fused by heat. The power generating element 57 issealed in a state in which the positive electrode tab 58 and thenegative electrode tab 59 are led to the outside. Herein, the powergenerating element 57 corresponds to the power generating element 21 ofthe lithium ion secondary battery 10 illustrated in FIG. 2 as describedabove. In the power generating element 57, plural single battery layers(single cell) 19, which are each formed of the positive electrode(positive electrode active substance layer) 13, the electrolyte layer 17and the negative electrode (negative electrode active substance layer)15, are laminated.

Meanwhile, the lithium ion secondary battery is not limited to a flatshape of laminate type. The winding type lithium ion secondary batterymay have a barrel shape or a flat and rectangular shape obtained bymodifying the barrel shape, and it is not particularly limited. As anouter casing material of the barrel shape, a laminate film can be used,and a barrel can (metal can) of a related art can be used, and thus itis not particularly limited. Preferably, the power generating element isencased with an aluminum laminate film. Weight reduction can be achievedwith such shape.

Furthermore, drawing of the tabs 58 and 59 illustrated in FIG. 3 is notparticularly limited, either. The positive electrode tab 58 and thenegative electrode tab 59 may be drawn from the same side or each of thepositive electrode tab 58 and negative electrode tab 59 may be dividedinto plural tabs and drawn from each side, and thus it is not limited tothe embodiment illustrated in FIG. 3. Furthermore, in a winding typelithium ion battery, it is also possible to form a terminal by using,for example, a barrel can (metal can) instead of a tab.

A typical electric vehicle has a battery storage space of about 170 L.Since a cell and an auxiliary machine such as a device for controllingcharge and discharge are stored in this space, storage space efficiencyof a cell is about 50% in general. The cell loading efficiency for thisspace is a factor of determining the cruising distance of an electricvehicle. As the size of a single cell decreases, the loading efficiencyis lowered, and thus it becomes impossible to maintain the cruisingdistance.

Thus, in the present invention, the battery structure of which powergenerating element is covered with an outer casing body preferably has alarge size. Specifically, length of short side of a laminate cellbattery is preferably 100 mm or more. Such large-size battery can beused for an automobile. Herein, the length of short side of a laminatecell battery indicates the length of a shortest side. The upper limit ofa length of a short side is, although not particularly limited,generally 400 mm or less.

[Volume Energy Density and Rated Discharge Capacity]

According to the market requirement, a typical electric vehicle needs tohave driving distance (cruising distance) of 100 km or more per singlecharge. Considering such cruising distance, the volume energy density ofa battery is preferably 157 Wh/L or more and the rated capacity ispreferably 20 Wh or more.

It is also possible to determine the large size of a battery in view ofa relationship between battery area or battery capacity, from theviewpoint of a large-sized battery, which is different from a physicalsize of an electrode. For example, in the case of a flat and stack typelaminate battery, for a battery with the ratio value of a battery area(projected area of a battery including an outer casing body of abattery) to rated capacity is 5 cm²/Ah or more, and with rated capacityof 3 Ah or more, the battery area per unit capacity is large so that aproblem of having lowered battery characteristics (cyclecharacteristics), which is caused by the collapse of the crystalstructure and so on accompanying expansion and shrinkage of an activesubstance, may occur more easily. As such, the non-aqueous electrolytesecondary battery according to this embodiment is preferably alarge-sized battery as described above from the viewpoint of having alarger merit obtained from exhibition of the working effects of thepresent invention. Furthermore, the aspect ratio of a rectangularelectrode is preferably 1 to 3, and more preferably 1 to 2. Meanwhile,the aspect ratio of an electrode is defined by longitudinal/transversalratio of a positive electrode active substance layer with a rectangularshape. By having the aspect ratio in this range, an advantage of havingboth the performances required for a vehicle and loading space can beobtained.

[Assembled Battery]

An assembled battery is formed by connecting plural batteries.Specifically, at least two of them are used in series, in parallel, orin series and parallel. According to arrangement in series or parallel,it becomes possible to freely control the capacity and voltage.

It is also possible to form a detachable small-size assembled battery byconnecting plural batteries in series or in parallel. Furthermore, byconnecting again plural detachable small-size assembled batteries inseries or parallel, an assembled battery having high capacity and highoutput, which is suitable for a power source or an auxiliary powersource for operating a vehicle requiring high volume energy density andhigh volume output density, can be formed. The number of the connectedbatteries for fabricating an assembled battery or the number of thestacks of a small-size assembled battery for fabricating an assembledbattery with high capacity can be determined depending on the capacityor output of a battery of a vehicle (electric vehicle) for which thebattery is loaded.

[Vehicle]

The non-aqueous electrolyte secondary battery of the present inventioncan maintain discharge capacity even when it is used for a long periodof time, and thus has good cycle characteristics. It also has highvolume energy density. For use in a vehicle such as an electric vehicle,a hybrid electric vehicle, a fuel cell electric vehicle, or a hybridfuel cell electric vehicle, long service life is required as well ashigh capacity and large size compared to use for an electric and mobileelectronic device. As such, the non-aqueous electrolyte secondarybattery can be preferably used as a power source for a vehicle, forexample, as a power source for operating a vehicle or as an auxiliarypower source for operating a vehicle.

Specifically, the battery or an assembled battery formed by combiningplural batteries can be mounted on a vehicle. According to the presentinvention, a battery with excellent long term reliability, outputcharacteristics, and long service life can be formed, and thus, bymounting this battery, a plug-in hybrid electric vehicle with long EVdriving distance and an electric vehicle with long driving distance percharge can be achieved. That is because, when the battery or anassembled battery formed by combining plural batteries is used for, forexample, a vehicle such as hybrid car, fuel cell electric car, andelectric car (including two-wheel vehicle (motor bike) or three-wheelvehicle in addition to all four-wheel vehicles (automobile, truck,commercial vehicle such as bus, compact car, or the like)), a vehiclewith long service life and high reliability can be provided. However,the use is not limited to a vehicle, and it can be applied to variouspower sources of other transportation means, for example, a movingobject such as an electric train, and it can be also used as a powersource for loading such as an uninterruptable power source device.

EXAMPLES

A description is made below in more detail in view of Examples andComparative Examples, but the present invention is not limited to theExamples given below.

Example 1

(1) Production of a Positive Electrode Active Substance

To an aqueous solution (1 mol/L) having nickel sulfate, cobalt sulfate,and manganese sulfate dissolved therein, sodium hydroxide and ammoniawere continuously supplied at 60° C. to adjust the pH to 11.3, andaccording to a co-precipitation method, metal composite hydroxide inwhich nickel, manganese, and cobalt were dissolved at molar ratio of50:30:20 was produced.

The metal composite hydroxide and lithium carbonate were weighed suchthat the molar ratio between the total mole number of metals other thanLi (Ni, Co, and Mn) and the mole number of Li was 1:1, and thenthoroughly mixed. The temperature was increased at temperature increaserate of 5° C./min, temporary calcination was performed at 900° C. for 2hours in air atmosphere, the temperature was increased at temperatureincrease rate of 3° C./min, and then main calcination was performed at920° C. for 10 hours. After cooling to room temperature, the NMCcomposite oxide (LiNi_(0.50)Mn_(0.30)Co_(0.20)O₂) was obtained.

The obtained NMC composite oxide was measured for the average particlediameter of primary particles (D1) and the crystallite diameter, andfrom the value of D1, the standard deviation (σ) of D1 and σ² wereobtained by calculation. Meanwhile, the measurement of D1 was performedas follows: focused ion beam (FIB) was used to cut a cross-section ofthe obtained NMC composite oxide, and the cross-sectional image wastaken by using a scanning type ion microscope (SIM). Furthermore, D2 canbe calculated as the average value of the diameter in long axisdirection of at least 50 secondary particles extracted. Meanwhile, asfor the D1, at least 200 primary particles were extracted and an averagevalue of the diameter in long axis direction thereof was calculated.Furthermore, the crystallite diameter was measured by Rietveld method bywhich a crystallite diameter is calculated from diffraction peakintensity obtained by powder X ray diffraction measurement.

Furthermore, the obtained NMC composite oxide was measured for tapdensity, BET specific surface area and peak intensity ratio(I(003)/I(104)) between the peak intensity (I(104)) of a (104) surfaceand the peak intensity (I(003)) of a (003) surface by powder X raydiffraction measurement. Meanwhile, for measuring the tap density, asample powder was added to a 10 ml glass mess cylinder, and aftertapping 200 times, powder filling density was measured. Furthermore, theBET specific surface area was measured by single point BET measurementbased on continuous fluidization which uses AMS8000 type fully automaticdevice for measuring powder specific surface area (manufactured byOhkura Riken Co., Ltd.) and uses nitrogen as the adsorption gas andhelium as the carrier gas. Specifically, the sample powder was heatedand deaerated at temperature of 150° C. by using mixed gas and cooled totemperature of liquid nitrogen to adsorb mixed gas of nitrogen/helium.Then, it was warmed to room temperature by using water to desorb theadsorbed nitrogen gas and the desorption amount was determined using athermal conductivity detector. A specific surface area of the sample wasthen calculated therefrom. Furthermore, for the powder X ray diffractionmeasurement to calculate the peak intensity ratio (I(003)/I(104)) andthe aforementioned crystallite diameter, a X ray diffractometer(manufactured by Rigaku Co., Ltd.) which uses Cu—Kα ray was used. Theanalysis was then performed by using the Fundamental Parameter. By usingX ray diffraction pattern obtained from a diffraction angle range of2θ=15 to 120° and the analysis software Topas Version 3, the analysiswas performed. As for the crystal structure, an assumption was made thatit belongs to hexagonal crystal of space group of R-3m in which Li ispresent in the 3a site, M (Ni, Co, Mn, Al, or the like) is present inthe 3b site, x of excess Li, and O is present in the 6c site, and thenthe crystallite diameter (Gauss) and crystal deformation (Gauss) wereobtained. Meanwhile, by assuming that isotropic temperature factor (Beq)is 1, refining was performed until Rwp<10.0, and GOF<1.3. As for theorder of refining, Beq was fixed at 1 and, while the z coordinate andsite occupancy ratio of oxygen, the crystallite diameter (Gauss), andbinding distance between sites remain as variables, the process wasrepeatedly performed until each variable shows no change.

(2) Production of a Positive Electrode

90% by weight of the positive electrode active substance obtained from(1), 5% by weight of ketjen black as a conductive aid (average particlediameter: 300 nm), 5% by weight of polyvinylidene fluoride (PVDF) as abinder, and a suitable amount of N-methyl-2-pyrrolidone (NMP) as asolvent for controlling slurry viscosity were admixed with one anotherto prepare a slurry of the positive electrode active substance. Then,the obtained slurry of the positive electrode active substance wascoated on an aluminum foil (thickness: 20 μm) as a current collector,dried for 3 minutes at 120° C., and subjected to press molding using aroll press machine to produce a positive electrode in which the coatingamount of the positive electrode active substance layer on a singlesurface is 18 mg/cm².

(3) Fabrication of a Coin Cell

Next, in a glove box under argon atmosphere, the positive electrodeobtained from above (2) was punched to a disc shape with diameter of 14mm to yield a positive electrode for a coin cell. As a negativeelectrode, metal lithium punched to a disc shape with diameter of 15 mmwas used. Furthermore, as an electrolyte solution, a solution containing1.0 M LiPF₆ dissolved in a mixed solvent of ethylene carbonate (EC) anddimethyl carbonate (DMC) (volume ratio of 1:1) was prepared. Thepositive electrode and the negative electrode were laminated via aseparator (material: polypropylene, thickness: 25 μm), charged to a coincell container, added with an electrolyte solution and covered with atop cover to produce a coin cell for evaluation. The produced batterywas maintained for 24 hours, and once the open circuit voltage (OCV) isstabilized, charging was performed to the cut off voltage of 4.25 V withcurrent density of 0.2 mA/cm² for the positive electrode to have theinitial charge capacity. Then, the capacity at the time of havingdischarge to cut off voltage of 3.0 V after resting for 1 hour was usedas the initial discharge capacity. Furthermore, this charge anddischarge cycle was repeated 200 times and the capacity retention ratewas obtained and evaluated as cycle durability. Results of theevaluation of each physical property and evaluation of the battery areshown in the Table 1 below. Meanwhile, the obtained coin cell wasdisintegrated in charged state at 4.25 V, and as a result of performingthe differential scanning calorimetry (DSC) of the positive electrode,the exothermic onset temperature was found to be 292° C.

Example 2

The NMC composite oxide (LiNi_(0.50)Mn_(0.30)Co_(0.20)O₂) wassynthesized in the same manner as the Example 1 described above exceptthat the conditions for the main calcination were changed to 930° C. and12 hours. As a result, a coin cell was produced and evaluation of eachphysical property and evaluation of a battery were performed. Theresults are shown in the Table 1 below.

Example 3

The NMC composite oxide (LiNi_(0.50)Mn_(0.30)Co_(0.20)O₂) wassynthesized in the same manner as the Example 1 described above exceptthat the conditions for the main calcination were changed to 935° C. and12 hours. As a result, a coin cell was produced and evaluation of eachphysical property and evaluation of a battery were performed. Theresults are shown in the Table 1 below.

Example 4

The NMC composite oxide (LiNi_(0.50)Mn_(0.30)Co_(0.20)O₂) wassynthesized in the same manner as the Example 1 described above exceptthat the conditions for the main calcination were changed to 940° C. and12 hours. As a result, a coin cell was produced and evaluation of eachphysical property and evaluation of a battery were performed. Theresults are shown in the Table 1 below.

Example 5

The NMC composite oxide (LiNi_(0.50)Mn_(0.30)Co_(0.20)O₂) wassynthesized in the same manner as the Example 1 described above exceptthat the conditions for the main calcination were changed to 940° C. and15 hours. As a result, a coin cell was produced and evaluation of eachphysical property and evaluation of a battery were performed. Theresults are shown in the Table 1 below.

Example 6

The NMC composite oxide (LiNi_(0.50)Mn_(0.30)Co_(0.20)O₂) wassynthesized in the same manner as the Example 1 described above exceptthat the conditions for the main calcination were changed to 950° C. and12 hours. As a result, a coin cell was produced and evaluation of eachphysical property and evaluation of a battery were performed. Theresults are shown in the Table 1 below.

Example 7

The NMC composite oxide (LiNi_(0.50)Mn_(0.30)Co_(0.20)O₂) wassynthesized in the same manner as the Example 1 described above exceptthat the conditions for the main calcination are changed to 980° C. and12 hours. As a result, a coin cell was produced and evaluation of eachphysical property and evaluation of a battery were performed. Theresults are shown in the Table 1 below.

Comparative Example 1

The NMC composite oxide (LiNi_(0.50)Mn_(0.30)Co_(0.20)O₂) wassynthesized in the same manner as the Example 1 described above exceptthat the conditions for the main calcination were changed to 1000° C.and 10 hours. As a result, a coin cell was produced and evaluation ofeach physical property and evaluation of a battery were performed. Theresults are shown in the Table 1 below.

Comparative Example 2

The NMC composite oxide (LiNi_(0.50)Mn_(0.30)Co_(0.20)O₂) wassynthesized in the same manner as the Example 1 described above exceptthat the conditions for the main calcination were changed to 1000° C.and 20 hours. As a result, a coin cell was produced and evaluation ofeach physical property and evaluation of a battery were performed. Theresults are shown in the Table 1 below.

TABLE 1 Conditions for Conditions for temporary main calcination AverageBET calcination for for producing particle Crystal- spe- I(003)/I(104)Capacity producing NMC NMC composite diameter lite cific Peak Inte-Initial retention composite oxide oxide of primary diam- Tap surfaceinten- grated discharge rate after Temper- Temper- particles σ² D1/σ²eter density area sity intensity capacity 200 cycles ature Time atureTime D1(μm) (μm)² 1/μm μm g/cm³ m²/g ratio ratio mAh/g % Example 1 900 2920 10 0.25 0.0050 50.4 0.10 2.65 0.23 1.70 1.16 167 97.1 Example 2 9002 930 12 0.29 0.0077 37.8 0.15 2.63 0.26 1.70 1.16 167 95.6 Example 3900 2 935 12 0.36 0.0086 41.4 0.27 2.32 0.48 1.62 1.14 167 92.1 Example4 900 2 940 12 0.48 0.0156 30.8 0.35 2.33 0.66 1.62 1.14 167 92.5Example 5 900 2 940 15 0.49 0.0204 24.2 0.37 2.19 0.40 1.28 1.08 16577.3 Example 6 900 2 950 12 0.62 0.0207 29.8 0.66 2.09 0.55 1.43 1.16166 88.4 Example 7 900 2 980 12 0.90 0.0315 28.6 0.95 2.22 0.27 1.371.14 160 85.3 Compar- 900 2 1000 10 1.1 0.0583 18.9 1.15 2.01 0.52 1.511.14 157 72.1 ative Example 1 Compar- 900 2 1000 20 2.3 0.1082 21.3 2.12.15 0.25 1.62 1.14 153 75.3 ative Example 2

From the above results, the Examples 1 to 7 in which the positiveelectrode active substance according to the present invention is usedexhibited higher capacity retention rate after 200 cycles compared tothe Comparative Examples 1 and 2, and thus they were found to haveexcellent cycle durability.

Example 8

Electrolytic manganese dioxide and aluminum hydroxide were admixed witheach other and subjected to a heating treatment at 750° C. to yieldmanganese (III) dioxide. After that, lithium carbonate was added andmixed such that Li/(Mn+Al) molar ratio was 0.55 followed by calcinationfor 20 hours at 850° C. to obtain a spinel lithium manganate.

Next, the spinel lithium manganate was added to have weight percentageof 5% by weight relative to 100% by weight of the NMC composite oxide(LiNi_(0.50)Mn_(0.30)Co_(0.20)O₂) which was produced in the same manneras the Example 1. It was then subjected to a mechanical treatment for 1hour by using a pulverizer. After that, it was calcined again for 10hours at 920° C. in air atmosphere to obtain powder of Li—Ni compositeoxide particles in which the spinel lithium manganate was coated in anamount of 5% by weight on the surface of secondary particles of theLiNi_(0.50)Mn_(0.30)Co_(0.20)O₂ as a nucleus (core). By using this Li—Nicomposite oxide as a positive electrode active substance, a coin cellfor evaluation was produced in the same manner as the Example 1, andthen capacity retention rate after 200 cycles was obtained and it wasevaluated as cycle durability. The results are shown in the Table 2below. Meanwhile, the obtained coin cell was disintegrated in chargedstate at 4.25 V, and as a result of performing the differential scanningcalorimetry (DSC) of the positive electrode, the exothermic onsettemperature was found to be 305° C.

Example 9

To an aqueous solution having nickel sulfate, cobalt sulfate, andmanganese sulfate dissolved therein, sodium hydroxide and ammonia weresupplied, and according to a co-precipitation method, metal compositehydroxide in which nickel, cobalt, and manganese were dissolved at molarratio of 1/3:1/3:1/3 was produced. The metal composite hydroxide andlithium carbonate were weighed such that the molar ratio between thetotal mole number of metals other than Li (Ni, Co, Mn) and the molenumber of Li was 1:1 and then thoroughly mixed. The temperature wasincreased at temperature increase rate of 5° C./min and calcination wasperformed at 920° C. for 10 hours in air atmosphere. After cooling toroom temperature, the LiNi_(1/3)Mn_(1/3)Co_(1/3)O₂ was added to haveweight percentage of 5% by weight relative to 100% by weight of the NMCcomposite oxide (LiNi_(0.50)Mn_(0.30)Co_(0.20)O₂) which was produced inthe same manner as the Example 1. It was then subjected to a mechanicaltreatment for 30 minutes by using a pulverizer. After that, it wascalcined again for 10 hours at 930° C. in air atmosphere to obtainpowder of Li—Ni composite oxide particles in whichLiNi_(1/3)Mn_(1/3)Co_(1/3)O₂ was coated in an amount of 5% by weight onthe surface of secondary particles of theLiNi_(0.50)Mn_(0.30)Co_(0.20)O₂ as a nucleus (core). By using this Li—Nicomposite oxide as a positive electrode active substance, a coin cellfor evaluation was produced in the same manner as the Example 1, andthen capacity retention rate after 200 cycles was obtained and it wasevaluated as cycle durability. The results are shown in the Table 2below. Meanwhile, the obtained coin cell was disintegrated in chargedstate at 4.25 V, and as a result of performing the differential scanningcalorimetry (DSC) of the positive electrode, the exothermic onsettemperature was found to be 295° C.

TABLE 2 Core-shell positive electrode material Capacity DSC AdditionInitial retention exothermic amount of discharge rate after onset shell(% by capacity 200 cycles temperature Core material Shell materialweight vs. core) mAh/g % ° C. Example 1 LiNi_(0.5)Mn_(0.3)CO_(0.2)O₂ — —167 97.1 292 Example 8 LiNi_(0.5)Mn_(0.3)CO_(0.2)O₂ Spinel lithium 5 16196.8 305 manganate Example 9 LiNi_(0.5)Mn_(0.3)CO_(0.2)O₂LiNi_(1/3)Mn_(1/3)CO_(1/3)O₂ 5 164 97.8 295

From the above results, the Example 8 and Example 9 using a core-shelltype positive electrode material which is obtained by forming a shellconsisting of spinel lithium manganate or LiNi_(1/3)Mn_(1/3)Co_(1/3)O₂around a core consisting of the positive electrode active substance ofthe present invention exhibit higher capacity retention rate after 200cycles compared to the Example 1, and thus are found to have moreexcellent cycle durability. Further, as the DSC exothermic onsettemperature is higher than that of the Example 1, it is also found thatthe effect of having more excellent heat stability is exhibited.

Example 10

A mixture of the NMC composite oxide (LiNi_(0.50)Mn_(0.30)Co_(0.20)O₂)which was produced in the same manner as the Example 1 and the spinellithium manganate which was produced in the same manner as the Example 8was used as a positive electrode active substance. At that time, themixing ratio of those materials was 90 : 10 (in terms of weight ratio ofNMC composite oxide: spinel lithium manganate) . Other than those, acoin cell for evaluation was produced in the same manner as the Example1, and then capacity retention rate after 200 cycles was obtained and itwas evaluated as cycle durability. Furthermore, the obtained coin shellwas charged at upper limit voltage of 4.25 V and constant current of 0.4mA/cm² at temperature conditions of −20° C., and constant currentdischarge was performed until discharge end voltage of 3.0 V. Afterthat, constant current charge was performed for the same coin cell atcurrent conditions of 4.0 mA/cm², and constant current discharge wasperformed until discharge end voltage of 3.0 V. Then, the ratio betweenthe capacity at the time of performing charge and discharge at currentconditions of 0.4 mA/cm² and the capacity at the time of performingcharge and discharge at current conditions of 4.0 mA/cm² was calculatedand evaluated as low temperature load characteristic (−20° C. outputcharacteristic). The results are shown in the Table 3 below.

Example 11

A coin cell for evaluation was produced in the same manner as theExample 10 except that the mixing ratio in the mixture of the NMCcomposite oxide (LiNi_(0.50)Mn_(0.30)Co_(0.20)O₂) and the spinel lithiummanganate was 70:30 (in terms of weight ratio of NMC compositeoxide:spinel lithium manganate), and then the capacity retention rateafter 200 cycles was obtained and evaluated as cycle durability.Furthermore, the low temperature load characteristic (−20° C. outputcharacteristic) was evaluated in the same manner as above. The resultsare shown in the Table 3 below.

Example 12

A coin cell for evaluation was produced in the same manner as theExample 10 except that the mixing ratio in the mixture of the NMCcomposite oxide (LiNi_(0.50)Mn_(0.30)Co_(0.20)O₂) and the spinel lithiummanganate was 30:70 (in terms of weight ratio of NMC compositeoxide:spinel lithium manganate), and then the capacity retention rateafter 200 cycles was obtained and evaluated as cycle durability.Furthermore, the low temperature load characteristic (−20° C. outputcharacteristic) was evaluated in the same manner as above. The resultsare shown in the Table 3 below.

TABLE 3 Mixing weight ratio of active substance Capacity −20° C. Output(% by weight) retention characteristics NMC Spinel Initial rate 4.0mA/cm² com- lithium discharge after 200 Capacity/0.4 posite manga-capacity cycles mA/cm² oxide nate mAh/g % Capacity Example 1 100 0 16797.1 0.62 Example 10 90 10 160 94.6 0.74 Example 11 70 30 147 91.6 0.89Example 12 30 70 120 82.5 0.98

It is shown from the above results that, compared to the Example 1, thecapacity retention rate after 200 cycles was slightly lower in theExamples 10 to 12 in which a positive electrode material formed bymixing the positive electrode active substance according to the presentinvention and spinel lithium manganate was used. However, the −20° C.output characteristic was improved. Based on this, it is found that thevoltage lowering under high output discharge at low temperature is lowso that deficient output of a vehicle is unlikely to occur even in acold area, for example.

Example 13

95 parts by mass of alumina particles (BET specific surface area: 5m²/g, average particle diameter: 2 μm) as inorganic particles and 5parts by mass of carboxymethyl cellulose as a binder (moisture contentper binder mass: 9.12% by mass, SUNROSE (registered trademark) MACseries, manufactured by NIPPON PAPER Chemicals CO., LTD.) werehomogeneously dispersed in water to prepare an aqueous solution. Thisaqueous solution was coated on both surfaces of a polyethylene (PE)microporous membrane (film thickness: 2 μm, porosity: 55%) by using agravure coater. Subsequently, it was dried at 60° C. to remove water toproduce a separator having a heat resistant insulating layer as amultilayer porous film with total film thickness of 25 μm, in which aheat resistant insulating layer is formed at 3.5 μm for both surfaces ofa microporous membrane. The weight per unit area of a heat resistantinsulating layer was 9 g/m² in a total of both surfaces.

(4) Production of Negative Electrode

Subsequently, 96.5% by weight of artificial graphite as a negativeelectrode active substance, 1.5% by mass of ammonium salt ofcarboxymethyl cellulose as a binder, and 2.0% by mass ofstyrene-butadiene copolymer latex were dispersed in purified water toproduce a slurry of negative electrode active substance. Then, thisslurry of negative electrode active substance was coated on a copperfoil (thickness: 10 μm) to be a negative electrode current collector,dried for 3 minutes at 120° C., and subjected to press molding using aroll press machine to produce a negative electrode. The same treatmentwas performed for the back surface to form a negative electrode activesubstance layer so that a negative electrode having a negative electrodeactive substance layer formed on both surfaces of the negative electrodecurrent collector (copper foil) was produced.

By alternately laminating, via the separator having a heat resistantinsulating layer obtained from above, a positive electrode obtained byforming the positive electrode produced in the Example 1 (2) on bothsurfaces of a positive electrode current collector (aluminum foil) and anegative electrode produced in above (4) (positive electrode 20 layersand negative electrode 21 layers) in the same manner as above, a powergenerating element was produced. The obtained power generating elementwas disposed within a bag made of aluminum laminate sheet as an outercasing, and an electrolyte solution was added thereto. As an electrolytesolution, a solution in which 1.0 M LiPF₆ was dissolved in a mixturesolvent of ethylene carbonate (EC) and dimethyl carbonate (DMC) (volumeratio of 1:1) was used. Subsequently, under vacuum conditions, theopening of the aluminum laminate sheet bag was sealed such that the tabfor taking out current, which is connected to both electrodes, was ledto outside, and a cell for test as a laminate type lithium ion secondarybattery with length of 280 mm×width of 210 mm×thickness of 7 mm wascompleted.

For evaluation of the characteristics of a separator attached to theobtained cell for test, the cell for test was kept for 1 hour in anincubator at 150° C. and shrinkage rate of the separator was measured toevaluate the heat resistant characteristic. For the measurement of thethermal shrinkage rate, the cell for test was kept for 1 hour in anincubator at 150° C. and then taken out. Then, the length of theseparator was measured, and the decrease ratio of the length compared tothe length before the test was used as the thermal shrinkage rate.Furthermore, as reliability test for the cell for test which wasobtained from above, the battery was kept in an incubator at 150° C. andthe time until the loss of the battery function was measured and thereliability test at high temperature was carried out. The results ofmeasuring thermal shrinkage rate and the results of the reliability testare shown in the Table 4 below. The produced battery had rated capacityof 56.6 Ah and the ratio of battery area to the rated capacity was 13.0cm²/Ah.

Example 14

A separator having a heat resistant insulating layer was obtained in thesame manner as the Example 13 except that the weight per unit area of aheat resistant insulating layer was adjusted to 13 g/m² in a total ofboth surfaces by modifying the coating gap of the gravure coater, andthe thermal shrinkage rate of the separator was measured in the samemanner as above. The measurement results are shown in the Table 4 below.

Furthermore, a cell for test was produced in the same manner as theExample 13 except that the obtained separator having a heat resistantinsulating layer was used, and the reliability evaluation was performedin the same manner as above. The results are shown in the Table 4 below.

Example 15

A separator having a heat resistant insulating layer was obtained in thesame manner as the Example 13 except that the weight per unit area of aheat resistant insulating layer was adjusted to 15 g/m² in a total ofboth surfaces by modifying the coating gap of the gravure coater, andthe thermal shrinkage rate of the separator was measured in the samemanner as above. The measurement results are shown in the Table 4 below.

Furthermore, a cell for test was produced in the same manner as theExample 13 except that the obtained separator having a heat resistantinsulating layer was used, and the reliability evaluation was performedin the same manner as above. The results are shown in the Table 4 below.

Example 16

A separator having a heat resistant insulating layer was obtained in thesame manner as the Example 13 except that the weight per unit area of aheat resistant insulating layer was adjusted to 17 g/m² in a total ofboth surfaces by modifying the coating gap of the gravure coater, andthe thermal shrinkage rate of the separator was measured in the samemanner as above. The measurement results are shown in the Table 4 below.

Furthermore, a cell for test was produced in the same manner as theExample 13 except that the obtained separator having a heat resistantinsulating layer was used, and the reliability evaluation was performedin the same manner as above. The results are shown in the Table 4 below.

Example 17

A separator having a heat resistant insulating layer was obtained in thesame manner as Example 13 except that the weight per unit area of a heatresistant insulating layer was adjusted to 5 g/m² in a total of bothsurfaces by modifying the coating gap of the gravure coater, and thethermal shrinkage rate of the separator was measured in the same manneras above. The measurement results are shown in the Table 4 below.

Furthermore, a cell for test was produced in the same manner as theExample 13 except that the obtained separator having a heat resistantinsulating layer was used, and the reliability evaluation was performedin the same manner as above. The results are shown in the Table 4 below.

Example 18

A separator having a heat resistant insulating layer was obtained in thesame manner as the Example 13 except that the weight per unit area of aheat resistant insulating layer was adjusted to 2 g/m² in a total ofboth surfaces by modifying the coating gap of the gravure coater, andthe thermal shrinkage rate of the separator was measured in the samemanner as above. The measurement results are shown in the Table 4 below.

Furthermore, a cell for test was produced in the same manner as theExample 13 except that the obtained separator having a heat resistantinsulating layer was used, and the reliability evaluation was performedin the same manner as above. The results are shown in the Table 4 below.

Example 19

The power generating element obtained from Example 13 was wound in awhirlpool shape to produce a wound electrode group. Then, the obtainedwound electrode group was crushed to have a flat shape, and then putinto an aluminum outer casing can with a thickness of 6 mm, a height of50 mm, and a width of 34 mm. After injecting an electrolyte solutionfollowed by sealing, a cell for test was produced as a lithium ionsecondary battery, and the reliability test was performed in the samemanner as above. The results are shown in the Table 4 below.

Example 20

With regard to the Example 19, polyethylene (PE) microporous membrane,which is a porous substrate before forming a heat resistant insulatinglayer on a separator having a heat resistant insulating layer, wasprovided by itself as a separator, and the thermal shrinkage rate wasmeasured in the same manner as above. Furthermore, by using thisseparator, a cell for test was produced in the same manner as theExample 13 described above, and the reliability test was performed inthe same manner as above. The results are shown in the Table 4 below.

Example 21

With regard to the Example 13, polyethylene (PE) microporous membrane,which is a porous substrate before forming a heat resistant insulatinglayer on a separator having a heat resistant insulating layer, wasprovided by itself as a separator, and the thermal shrinkage rate wasmeasured in the same manner as above. Furthermore, by using thisseparator, a cell for test was produced in the same manner as theExample 13 described above, and the reliability test was performed inthe same manner as above. The results are shown in the Table 4 below.

TABLE 4 Weight per Evaluation of unit area of reliability heat resistantMinutes (time insulating Thermal until lowered layer shrinkage ratebattery Cell type g/m² % voltage) Example 13 Laminate 9 8 >60 Example 14Laminate 13 7 >60 Example 15 Laminate 15 7 >60 Example 16 Laminate 177 >60 Example 17 Laminate 5 10 50 Example 18 Laminate 2 15 35 Example 19Can 9 8 >60 Example 20 Can 0 20 15 Example 21 Laminate 0 30 10

From the results described above, it is shown that the thermal shrinkagerate is lower in the Examples 13 to 19 in which a separator (so-calledceramic separator) having a heat resistant insulating layer (ceramiclayer) on a surface is used, compared to the Example 20 and Example 21in which no such separator is used. It is also found that the results ofthe reliability evaluation are improved. Furthermore, this effectexhibited by using a ceramic separator (decrease ratio of thermalshrinkage rate and improvement in reliability evaluation) is moresignificantly shown in a flat stack type laminate battery using alaminate film than a winding type battery in which an outer casing canis used as an outer casing body of a battery.

The present application is based on Japanese Patent Application No.2013-040108 filed on Feb. 28, 2013, and its disclosure is entirelyincorporated herein by reference.

REFERENCE SIGNS LIST

-   1 Shell part of positive electrode material-   2 Core part of positive electrode material-   3 Positive electrode material-   10, 50 Lithium ion secondary battery-   11 Positive electrode current collector-   12 Negative electrode current collector-   13 Positive electrode active substance layer-   15 Negative electrode active substance layer-   17 Separator-   19 Single battery layer-   21, 57 Power generating element-   25 Positive electrode current collecting plate-   27 Negative electrode current collecting plate-   29, 52 Battery outer casing material-   58 Positive electrode tab-   59 Negative electrode tab

The invention claimed is:
 1. A positive electrode active substance for anon-aqueous electrolyte secondary battery comprising a composite oxidecontaining lithium and nickel, wherein the positive electrode activesubstance has a structure of secondary particles formed by aggregationof primary particles, the average particle diameter of primary particles(D1) is 0.9 μm or less, the average particle diameter of the primaryparticles (D1) and the standard deviation (σ) of the average particlediameter of the primary particles (D1) meet the relationship ofD1/σ²≧24, and the tap density of the positive electrode active substanceis 2.3g/cm³ or more.
 2. The positive electrode active substanceaccording to claim 1, wherein the composite oxide comprises acomposition represented by General Formula:Li_(a)Ni_(b)Mn_(c)Co_(d)M_(x)O₂, with the proviso that, in the formula,a, b, c, d, and x satisfy 0.9≦a≦1.2, 0<b<1, 0<c≦0.5, 0<d≦0.5, 0≦x≦0.3,and b+c+d=1; and M represents at least one selected from the groupconsisting of Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, and Cr.
 3. Thepositive electrode active substance according to claim 2, wherein b, cand d are as follows: 0.44≦b≦0.51, 0.27≦c≦0.31, and 0.19≦d≦0.26.
 4. Thepositive electrode active substance according to claim 1, wherein thecrystallite diameter of the positive electrode active substance is 0.4μm or less.
 5. The positive electrode active substance according toclaim 1, wherein the BET specific surface area of the positive electrodeactive substance is 0.1 to 1.0 m²/g.
 6. The positive electrode activesubstance according to claim 1, wherein the diffraction peak of a (104)surface and the diffraction peak of a (003) surface of the positiveelectrode active substance obtained by powder X ray diffractionmeasurement have a diffraction peak intensity ratio ((003)/(104)) of1.28 or more and a diffraction peak integrated intensity ratio((003)/(104)) of 1.05 or more.
 7. A positive electrode material for anon-aqueous electrolyte secondary battery, the positive electrodematerial comprising: a core part comprising the positive electrodeactive substance according to claim 1; and a shell part comprising alithium-containing composite oxide which is different from the positiveelectrode active substance.
 8. A positive electrode material for anon-aqueous electrolyte secondary battery, the positive electrodematerial being formed as a mixture of the positive electrode activesubstance according to claim 1 and a spinel type manganese positiveelectrode active substance.
 9. The positive electrode material accordingto claim 8, wherein the mixing weight ratio of the positive electrodeactive substance and the spinel type manganese positive electrode activesubstance is 50:50 to 90:10.
 10. A positive electrode for a non-aqueouselectrolyte secondary battery, the positive electrode being obtained byforming, on a surface of a positive electrode current collector, apositive electrode active substance layer containing at least oneselected from the group consisting of the positive electrode activesubstance according to claim 1 and a positive electrode material beingformed as a mixture of the positive electrode active substance and aspinel type manganese positive electrode active substance.
 11. Anon-aqueous electrolyte secondary battery comprising a power generatingelement comprising: the positive electrode according to claim 10, anegative electrode obtained by forming a negative electrode activesubstance layer on a surface of a negative electrode current collector,and a separator.
 12. The non-aqueous electrolyte secondary batteryaccording to claim 11, wherein the separator is a separator having aheat resistant insulating layer.
 13. The non-aqueous electrolytesecondary battery according to claim 11, wherein the ratio value of abattery area, projected area of a battery including an outer casing bodyof a battery to rated capacity is 5 cm²/Ah or more and the ratedcapacity is 3 Ah or more.
 14. The non-aqueous electrolyte secondarybattery according to claim 11, wherein the aspect ratio of an electrodedefined as a longitudinal/transversal ratio of a rectangular positiveelectrode active substance layer is 1 to 3.